Isobutylene polymerization in the presence of t-BuCl/SnCl4

Summary The effect of tert-butyl chloride in the polymerizations of isobutylene carried out in the presence of SnCl₄ in dichloromethane at temperatures-20°C and-78°C was investigated. Synthesized polyisobutylene samples showed a bimodal molecular weight distribution (MWD) and it was found that the weight content of the lowermolecular weight (LMW) fraction increased with increasing t-BuCl concentration in the polymerization mixture. The effect of ageing of the initiation mixture t-BuCl/SnCl₄ in CH₂Cl₂ prepared in advance on MWD of the PIB samples was also studied. Ageing of the initiation system supports the formation of the LMW fraction and this oily PIB is the only product of the polymerization at-20°C, .     

Expert judgement on the long term possibilities of conventional emission abatement technologies for passenger cars

Topics in Catalysis - This paper presents the results of a quantitatively substantiated “expert judgement” concerning the potential for further reduction of the exhaust emissions of...     

Reactive‐extrusion route for the closed‐loop recycling of poly(ethylene terephthalate)

The effectiveness of the reactive extrusion technique was investigated for poly(ethylene terephthalate) to promote the concept of closed‐loop recycling, that is, the reuse of waste material in the initial application. More specifically, a chain‐extender system, consisting of pyromellitic dianhydride, polyol, and a catalyst, was employed, and its efficiency regarding the improvement of the recyclate quality was evaluated. Accordingly, rheological and thermal characterizations were performed and used as criteria of the modification induced in the polymer molecular structure during processing due to the counteracting degradation and chain‐extension reactions. In particular, the molecular weight, related to intrinsic viscosity and melt flow rate measurements, of modified poly(ethylene terephthalate) samples was found to increase with the additive content. Simultaneously, a decrease in the crystallinity was observed, attributed to the branching effect of the chain extender, which restricted the ability of the macromolecules to organize in the crystal structure. Beyond a critical concentration of the additive system, the molecular weight of the treated samples started to decrease again, and this was accompanied by a small increase in the crystallinity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1671–1678, 2007     

On a generalization of Bernstein polynomials and Bézier curves based on umbral calculus

In Winkel (2001) a generalization of Bernstein polynomials and Bézier curves based on umbral calculus has been introduced. In the present paper we describe new geometric and algorithmic properties of this generalization including: (1) families of polynomials introduced by Stancu (1968) and Goldman (1985), i.e., families that include both Bernstein and Lagrange polynomial, are generalized in a new way, (2) a generalized de Casteljau algorithm is discussed, (3) an efficient evaluation of generalized Bézier curves through a linear transformation of the control polygon is described, (4) a simple criterion for endpoint tangentiality is established.     

Studies on miscibility in homopolymer/ random copolymer blends by equation of state theory

The miscibility of poly(methyl methacrylate) (PMMA) and styrene-acrylonitrile random copolymers (SAN) blends was investigated on the basis of the Flory—Orwoll—Vrij equation of state theory. To obtain the equation of state parameters (P*, V*_sp, T*: characteristic parameters), the pressure—volume—temperature (PVT) behaviour was measured for PMMA and a series of SANs with various acrylonitrile contents. The exchange energy parameter X_ij was also calculated by fitting the theory to some phase diagrams of PMMA/SAN blends. The Flory—Huggins interaction parameter χ was separated into two contributions based on the equation of state theory for mixtures: the exchange energy term χ_inter and the free volume term χ_free. Both the temperature and copolymer composition dependences of χ_inter and χ_free were estimated by calculations using the equation of state parameters. There exists a region in which χ_inter is negative, leading to a miscibility window in PMMA/SAN blends. However, the immiscibility at high temperatures in the blends cannot be explained only by χ_inter; it is caused by the free volume contribution, χ_free. The miscibility window behaviour in PMMA/SAN blends may be explained within the framework of the equation of state theory.     

Allelochemical resistance of bald cypress,Taxodium distichum,heartwood to the subterranean termite,Coptotermes formosanus

The heartwood of bald cypress,Taxodium distichum (L.) Rich., resisted feeding attack by the Formosan subterranean termite,Coptotermes formosanus Shiraki. Hexane-extracted heartwood, however, was consumed at > 12 times the amount of sound heartwood eaten. A bioassay usingT. distichum sapwood as a feeding substrate was employed to assess the antitermitic activity of successive hexane, acetone, and methanol extracts of heartwood shavings and isolates derived from the active hexane extract. Two fractions, eluted from the crude hexane extract by liquid chromatography, significantly reduced termite feeding compared to the parent extract, while a third fraction was less active than the original hexane extract. Each fraction contained one major component. All three components were structurally related diterpenes. The two most active heartwood constituents were identified by GC-MS and NMR as ferruginol and manool, while the third and least active, but most prevalent, compound in heartwood was identified as nezukol. Results of bioassays suggest that these allelochemicals act principally as feeding deterrents with accompanying termite mortality due to starvation.     

Optimizing Safe Yield Policy Implementation

The presented method enhances groundwater-mandated safe yield management. It is useful for settings that prevent sustained yield or integrated management. To protect hydraulically connected surface water rights, the Utah government’s Cache Valley groundwater management plan proposes that total pumping increase not exceed 84,431 m³/day. To determine how best to spatially distribute additional allowable pumping, stakeholders quantified limits defining acceptable impacts on selected water resource indicators. A new simulation–optimization (S–O) algorithm used these limits while computing optimal spatially distributed perennial yield or safe yield groundwater pumping extraction strategies. The limits prevent unacceptable decreases in: head and net flow between aquifer and surface waters (rivers, surface/subsurface drains, springs, lakes). The optimization objective function maximizes weighted pumping to provide water for 18 growing municipalities. For 16 perennial yield scenarios, computed optimal pumping increases differ in protectiveness toward senior water rights, and range from 16% to 103% of the state plan-proposed increase. Implementing a protective strategy would achieve 90% of the storage changes needed to reach equilibrium within 23 years. Indicator potentiometric heads would reach equilibrium within 10–40 years. At equilibrium, an optimal Cache Valley perennial yield strategy acceptably minimizes net annual non-pumping discharges. By comparison, multi-period 20-year transient groundwater mining optimizations allow more pumping in early years. Pumping then must decline to satisfy seepage and head constraints through year 20. Adverse seepage impact would increase for years thereafter. For situations governed by safe or perennial yield policy, equilibrium-based (steady-state) optimization is very useful. It effectively develops optimal perennial yield strategies.     

Differences in cytocompatibility,dynamics of the oxide layers’ formation,and nickel release between superelastic and thermo-activated nickel–titanium archwires

Superelastic (SE) and thermo-activated (TA) nickel–titanium (NiTi) archwires are used in everyday orthodontic practice, based on their acceptable biocompatibility and well-defined shape memory properties. However, the differences in their surface microstructure and cytotoxicity have not been clearly defined, and the standard cytotoxicity tests are too robust to detect small differences in the cytotoxicity of these alloys, all of which can lead to unexpected adverse reactions in some patients. Therefore, we tested the hypothesis that the differences in manufacture and microstructure of commercially available SE and TA archwires may influence their biocompatibility. The archwires were studied as-received and after conditioning for 24 h or 35 days in a cell culture medium under static conditions. All of the tested archwires, including their conditioned medium (CM), were non-cytotoxic for L929 cells, but Rematitan SE (both as received and conditioned) induced the apoptosis of rat thymocytes in a direct contact. In contrast, TruFlex SE and Equire TA increased the proliferation of thymocytes. The cytotoxic effect of Rematitan SE correlated with the higher release of Ni ions in CM, higher concentration of surface Ni and an increased oxygen layer thickness after the conditioning. In conclusion, the apoptosis assay on rat thymocytes, in contrast to the less sensitive standard assay on L929 cells, revealed that Rematitan SE was less cytocompatible compared to other archwires and the effect was most probably associated with a higher exposition of the cells to Ni on the surface of the archwire, due to the formation of unstable oxide layer.